JP2535218B2 - Self-activated zinc oxide phosphor - Google Patents
Self-activated zinc oxide phosphorInfo
- Publication number
- JP2535218B2 JP2535218B2 JP1050456A JP5045689A JP2535218B2 JP 2535218 B2 JP2535218 B2 JP 2535218B2 JP 1050456 A JP1050456 A JP 1050456A JP 5045689 A JP5045689 A JP 5045689A JP 2535218 B2 JP2535218 B2 JP 2535218B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- sulfur
- zinc oxide
- self
- zno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/10—Geothermal energy
Landscapes
- Luminescent Compositions (AREA)
- Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)
Description
本発明は、主として、蛍光表示管やフライングスポッ
ト管に使用される自己付活酸化亜鉛蛍光体に関する。The present invention mainly relates to a self-activated zinc oxide phosphor used for a fluorescent display tube or a flying spot tube.
自己付活酸化亜鉛蛍光体は、習慣的にZnO:Znと書かれ
ている。この蛍光体は、導電性があるために、蛍光表示
管用として重要である。低速電子線で刺激されて、青緑
色に発光し、優れた発光特性を有する。Self-activated zinc oxide phosphors are customarily written as ZnO: Zn. Since this phosphor has conductivity, it is important for a fluorescent display tube. When stimulated by a slow electron beam, it emits blue-green light and has excellent emission characteristics.
ZnO:Zn蛍光体は、母体構成元素と同じ亜鉛を付活剤と
するため、付活剤のZnを特定することが困難である。こ
のことは本蛍光体の特性を改良することを著しく難しく
している。 この蛍光体の製造においては、製造者が経験で、焼成
雰囲気を調整して付活剤となるZn量を特定している。す
なわち、熟練者の勘が、本蛍光体の性能を左右する重要
な要件となっている。従って、安定して優れた特性のZn
O:Zn蛍光体を製造することは、極めて困難を伴ってい
た。 このため、発光効率が高く、しかも、寿命特性の優れ
た自己付活酸化亜鉛蛍光体を安定に製造できる技術開発
が切望されていた。 本発明はこの要求に答えるために開発されたものであ
る。この発明の重要な目的は、発光効率、並びに寿命特
性ともに優れ、しかも安定に製造できるZnO:Zn蛍光体を
提供することにある。Since the ZnO: Zn phosphor uses the same zinc as the matrix constituent element as the activator, it is difficult to specify Zn of the activator. This makes it extremely difficult to improve the properties of the present phosphor. In the manufacture of this phosphor, the manufacturer has experienced that the firing atmosphere is adjusted to specify the Zn amount serving as the activator. That is, the intuition of a skilled person is an important factor that influences the performance of the present phosphor. Therefore, Zn with stable and excellent characteristics
Manufacturing an O: Zn phosphor has been extremely difficult. Therefore, there has been a strong demand for the development of a technique capable of stably producing a self-activated zinc oxide phosphor having high luminous efficiency and excellent life characteristics. The present invention was developed to meet this need. An important object of the present invention is to provide a ZnO: Zn phosphor that is excellent in luminous efficiency and life characteristics and can be stably manufactured.
本発明のZnO:Zn蛍光体は、共付活剤としてイオウを導
入している。一定量のイオウを導入することにより、付
活量を特定して発光効率を制御している。The ZnO: Zn phosphor of the present invention incorporates sulfur as a co-activator. By introducing a fixed amount of sulfur, the activation amount is specified to control the luminous efficiency.
酸化亜鉛蛍光体の発光輝度を高めるために最も大きな
要因は、発光中心の濃度と、結晶内における発光中心の
幾何学的な配置である。発光中心は、多すぎても、少な
すぎても発光輝度が低下する。それは、発光中心が多す
ぎると濃度消光が起こり、反対に少ないと発光効率が減
少することが理由である。 また、発光中心の結晶内における幾何学的な配列が、
理想的な結晶の配列に比較して偏っていると、高い発光
輝度が得られないことも究明されている。 発光中心の幾何学的配列を制御できるなら、高い発光
効率を維持できる。 本発明者等は種々の実験を繰り返した結果、ZnO:Zn蛍
光体の母体中に、イオウを適量導入させることにより、
発光効率、ひいては発光中心の量と、結晶内への配置を
制御できることを見いだした。 イオウ（Ｓ）は、付活剤となる亜鉛量と、付活剤の結
晶内への適正配置を助ける働きをし、しかも、一部はZn
O:Znの結晶構造に含有される。イオン（Ｓ）の含有量
は、好ましくは、100PPm以下の調整される。さらに好ま
しくは、イオウ（Ｓ）の含有量を、５〜50ppmの範囲に
調整すると、ZnO:Zn蛍光体は、最も発光効率が高くな
る。 第１図に、イオウ（Ｓ）の含有量に対するZnO:Zn蛍光
体の相対発光輝度を示す。この図に示すように、イオウ
（Ｓ）の含有量が10ppm以下の範囲では、イオウ（Ｓ）
の含有量が多くなるほど、発光輝度が高くなる。イオウ
（Ｓ）の含有量が10ppm以上になると発光輝度は次第に
低下する。 ただし、第１図はイオウ（Ｓ）を含まないZnO:Zn蛍光
体の輝度を100％として、相対発光輝度を測定してい
る。The most important factors for increasing the emission brightness of the zinc oxide phosphor are the concentration of the emission centers and the geometrical arrangement of the emission centers in the crystal. If the number of luminescent centers is too large or too small, the luminescent brightness will decrease. The reason is that the concentration quenching occurs when there are too many emission centers, and conversely, when there are few emission centers, the emission efficiency decreases. In addition, the geometrical arrangement of the emission center in the crystal is
It has also been clarified that a high emission luminance cannot be obtained if the crystal array is biased compared to the ideal crystal arrangement. If the geometrical arrangement of emission centers can be controlled, high emission efficiency can be maintained. The present inventors have repeated various experiments, ZnO: in the matrix of the phosphor, by introducing an appropriate amount of sulfur,
It was found that the luminous efficiency, and thus the amount of luminescent centers and the arrangement in the crystal can be controlled. Sulfur (S) functions to help the amount of zinc that acts as an activator and the proper placement of the activator in the crystal.
It is contained in the crystal structure of O: Zn. The content of ions (S) is preferably adjusted to 100 PPm or less. More preferably, when the content of sulfur (S) is adjusted within the range of 5 to 50 ppm, the ZnO: Zn phosphor has the highest luminous efficiency. FIG. 1 shows the relative emission brightness of the ZnO: Zn phosphor with respect to the sulfur (S) content. As shown in this figure, when the content of sulfur (S) is 10ppm or less, sulfur (S) is
The higher the content of, the higher the emission brightness. When the sulfur (S) content is 10 ppm or more, the emission brightness gradually decreases. However, in FIG. 1, the relative emission brightness is measured with the brightness of the ZnO: Zn phosphor containing no sulfur (S) as 100%.
以下、実施例について説明するが、本発明は実施例に
限られるものではない。 ［実施例１］ 蛍光体原料として、 ZnCO3……1kg ZnS………5g 混合する。 混合物を石英ルツボに充填し、ルツボを焼成炉に入れ
て焼成する。 焼成工程においては、焼成炉内に、体積比で、98:2の
比率で、窒素ガスと水素ガスとが混合された気体を供給
し、この混合ガス雰囲気で、２時間還元焼成する。焼成
温度は、850℃とした。 その後、焼成品をルツボから取り出してほぐし、水洗
いした後、分離して乾燥する。 得られた自己付活酸化亜鉛蛍光体は、10ppmのイオウ
（Ｓ）を含有していた。また、この蛍光体は、ZnSを添
加しない以外、同様にして焼成した従来のZnO:Zn蛍光体
に比較して、相対発光輝度が約60％向上した。相対発光
輝度は、低速電子線ディマンタブル装置にて50V、1mAの
条件で輝度を測定した。 ［実施例２〜９］ ZnSの添加量を調整する以外、実施例１と同様にしてZ
nO:Zn蛍光体を製造した。 ZnSの添加量は、ZnCO3を1kgに対して、1g、3g、10g、
15g、17g、20g、25g、30gとした。 得られたZnO:Zn蛍光体は、第１表に示すように、順番
にイオウ（Ｓ）の含有量が、1.1ppm、5.2ppm、21ppm、3
2ppm、42ppm、55ppm、75ppm、93ppmとなり、相対発光輝
度が順番に、110％、155％、177％、180％、172％、152
％、123％、105％となった。 Examples will be described below, but the present invention is not limited to the examples. [Example 1] As a phosphor material, ZnCO 3 ... 1 kg ZnS ... 5 g was mixed. A quartz crucible is filled with the mixture, and the crucible is put into a firing furnace and fired. In the firing step, a gas in which nitrogen gas and hydrogen gas are mixed is supplied into the firing furnace in a volume ratio of 98: 2, and reduction firing is performed for 2 hours in this mixed gas atmosphere. The firing temperature was 850 ° C. Then, the fired product is taken out from the crucible, disentangled, washed with water, separated and dried. The obtained self-activated zinc oxide phosphor contained 10 ppm of sulfur (S). Further, this phosphor has a relative emission luminance improved by about 60% as compared with the conventional ZnO: Zn phosphor fired in the same manner except that ZnS is not added. The relative emission brightness was measured by a low-speed electron beam demantable device under the conditions of 50 V and 1 mA. [Examples 2 to 9] Z was performed in the same manner as in Example 1 except that the addition amount of ZnS was adjusted.
An nO: Zn phosphor was manufactured. The amount of ZnS added is 1 g of ZnCO 3 , 1 g, 3 g, 10 g,
The amounts were 15 g, 17 g, 20 g, 25 g and 30 g. As shown in Table 1, the obtained ZnO: Zn phosphors contained sulfur (S) in the order of 1.1 ppm, 5.2 ppm, 21 ppm, 3 ppm.
It becomes 2ppm, 42ppm, 55ppm, 75ppm, 93ppm, and relative emission brightness is 110%, 155%, 177%, 180%, 172%, 152 in order.
%, 123%, and 105%.
本発明の自己付活酸化亜鉛蛍光体は、ZnO:Zn蛍光体の
母体中に、イオウを導入して、発光中心の量と、結晶内
への配置を制御する。イオウは、付活剤となる亜鉛の量
と、付活剤の結晶内への適正配置を助ける働きをする。
また、イオウの一部はZnO:Znの結晶構造に含有される。
イオウを含むZnO:Zn蛍光体の相対発光輝度は、第１表と
第１図とに示すように、従来品に比較して飛躍的に向上
する。In the self-activated zinc oxide phosphor of the present invention, sulfur is introduced into the matrix of the ZnO: Zn phosphor to control the amount of emission centers and the arrangement in the crystal. Sulfur serves to help the amount of zinc activator and the proper placement of the activator within the crystals.
In addition, part of sulfur is contained in the ZnO: Zn crystal structure.
As shown in Table 1 and FIG. 1, the relative emission brightness of the ZnO: Zn phosphor containing sulfur is remarkably improved as compared with the conventional product.
第１図はイオウ含有量に対する輝度の変化を示すグラフ
である。FIG. 1 is a graph showing changes in luminance with respect to sulfur content.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 内村 勝典 徳島県阿南市上中町岡491番地100 日亜 化学工業株式会社内 (56)参考文献 特開 昭60−92385（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsunori Uchimura 491-1 Oka, Kaminaka-cho, Anan City, Tokushima Prefecture Nichia Chemical Industry Co., Ltd. (56) References JP-A-60-92385 (JP, A)
Claims (1)
することを特長とする自己付活酸化亜鉛蛍光体。1. A self-activating zinc oxide phosphor characterized by containing 1 to 100 PPm of sulfur in a phosphor matrix.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1050456A JP2535218B2 (en) | 1989-03-01 | 1989-03-01 | Self-activated zinc oxide phosphor |
| JP5160378A JPH07116425B2 (en) | 1989-03-01 | 1993-06-03 | Method for producing self-activated zinc oxide phosphor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1050456A JP2535218B2 (en) | 1989-03-01 | 1989-03-01 | Self-activated zinc oxide phosphor |
| JP5160378A JPH07116425B2 (en) | 1989-03-01 | 1993-06-03 | Method for producing self-activated zinc oxide phosphor |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5160378A Division JPH07116425B2 (en) | 1989-03-01 | 1993-06-03 | Method for producing self-activated zinc oxide phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02228389A JPH02228389A (en) | 1990-09-11 |
| JP2535218B2 true JP2535218B2 (en) | 1996-09-18 |
Family
ID=26390926
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1050456A Expired - Lifetime JP2535218B2 (en) | 1989-03-01 | 1989-03-01 | Self-activated zinc oxide phosphor |
| JP5160378A Expired - Lifetime JPH07116425B2 (en) | 1989-03-01 | 1993-06-03 | Method for producing self-activated zinc oxide phosphor |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5160378A Expired - Lifetime JPH07116425B2 (en) | 1989-03-01 | 1993-06-03 | Method for producing self-activated zinc oxide phosphor |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP2535218B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19626219A1 (en) * | 1996-06-29 | 1998-01-02 | Philips Patentverwaltung | Phosphor preparation with SiO¶2¶ particle coating |
| EP1630218B1 (en) | 2003-04-30 | 2014-08-20 | National Institute for Materials Science | Zinc oxide phosphor and process for producing the same |
| CN101775278B (en) * | 2010-01-28 | 2013-10-16 | 海洋王照明科技股份有限公司 | Colloid-coating fluorescent powder and preparation method thereof |
| CN102234512B (en) * | 2010-04-30 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method of modified luminescent material |
| EP3480279A4 (en) * | 2016-06-30 | 2020-01-01 | Sakai Chemical Industry Co., Ltd. | Zinc oxide phosphor and method for producing same |
-
1989
- 1989-03-01 JP JP1050456A patent/JP2535218B2/en not_active Expired - Lifetime
-
1993
- 1993-06-03 JP JP5160378A patent/JPH07116425B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02228389A (en) | 1990-09-11 |
| JPH07116425B2 (en) | 1995-12-13 |
| JPH0693259A (en) | 1994-04-05 |
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